CN1119587C - 冷冻装置 - Google Patents

冷冻装置 Download PDF

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CN1119587C
CN1119587C CN97122979A CN97122979A CN1119587C CN 1119587 C CN1119587 C CN 1119587C CN 97122979 A CN97122979 A CN 97122979A CN 97122979 A CN97122979 A CN 97122979A CN 1119587 C CN1119587 C CN 1119587C
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cooling agent
refrigerator oil
oil
freezing plant
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CN1187603A (zh
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须永高史
渡邊正人
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Sanyo Electric Co Ltd
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Sanyo Electric Co Ltd
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • C10M171/008—Lubricant compositions compatible with refrigerants
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
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    • F25B9/00—Compression machines, plants or systems, in which the refrigerant is air or other gas of low boiling point
    • F25B9/002—Compression machines, plants or systems, in which the refrigerant is air or other gas of low boiling point characterised by the refrigerant
    • F25B9/006—Compression machines, plants or systems, in which the refrigerant is air or other gas of low boiling point characterised by the refrigerant the refrigerant containing more than one component
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Abstract

本发明是在使用不含氯的氟代烃类致冷剂单体或其混合致冷剂进行冷冻循环，并封装入一种与所说致冷剂具有相溶性的冷冻机油而构成的冷冻装置，其中上述冷冻机油以由下述通式(1)表示的构成单元的聚乙烯醚类化合物为主成分(式中，R1～R3可以相同或不同地各自表示氢原子或碳数1～8的烃基)。

Description

冷冻装置
本发明涉及冷冻装置，该冷冻装置使用1，1，1，2-四氟乙烷(以下称为R134a)等不含氯的氟代烃类致冷剂单体或混合致冷剂进行冷冻循环并使用以聚乙烯醚油作为基础油的冷冻机油。
冷藏库、自动售货机和陈列柜用的压缩机过去多数都是使用二氯二氟甲烷(以下称为R12)作为致冷剂。由于这种R12存在破坏臭氧层的问题，因此被作为氟里昂规定的对象。于是，人们研究在冷冻机中使用以R134a为代表的不含氯的氟代烃类致冷剂(HFC、FC)作为R12的代替致冷剂(例如，参照特开平1-271491公报)。
然而，致冷剂R134a与现在使用的矿物油或烷基苯油等冷冻机油的相溶性差，使得冷冻机油向压缩机回流的性能劣化，或者使得在停止状态下突然起动时把分离的致冷剂吸上，由于这样一些原因，导致了压缩机润滑不良的问题。
为此，本发明者们对一种多元醇酯类油作为与致冷剂R134a具有相溶性的冷冻机油进行了研究。然而，我们发现这类多元醇酯油在用于致冷剂压缩机时会由于热分解而生成脂肪酸，这些脂肪酸会引起滑动部件的腐蚀，从而使其磨损。
于是，本发明者们把作为致冷剂的R134a与作为冷冻机油的多元醇酯类油组合起来用于致冷剂压缩机并对此进行了深入的研究，结果发现，除了上述问题之外，多元醇酯类油还会由于水分的影响而引起水解，从而使总酸值上升，并且由于金属皂的生成并变成淤渣，从而对冷冻循环产生不良影响，另外由于氧或氯的作用而引起分解、氧化劣化和聚合反应，以及由于金属皂或高分子淤渣的生成而对冷冻循环产生不良影响。
另一方面，虽然已知聚亚氧烷基乙二醇类油不会引起水解等反应，因此不需那样严格的管理，但是由于它的绝缘性差，因此，将其直接用于这种内藏电动机的致冷剂压缩机是不适宜的。
从而，本发明者们发现，通过向一种特殊组成的聚乙烯醚油中加入特定的添加剂等，将其与特定的HFC类致冷剂组合并通过特定的控制，即可以解决上述的问题。
本发明解决上述的问题，目的是解决使用一种与不含氯的氟代烃类致冷剂(例如R134a)具有相溶性的聚乙烯醚类油作为冷冻机油使用时的上述问题，获得一种良好的冷冻装置。
如权利要求1所述，本发明是一种冷冻装置，它使用不含氯的氟代烃类致冷剂单体或其混合致冷剂进行冷冻循环，并将一种与所说致冷剂具有相溶性的冷冻机油封装入而构成，其中，上述冷冻机油以一种具有由下述通式(1)表示的构成单元的聚乙烯醚类化合物为主成分，并且在每一构成单元中，R4的构成比为，碳数1～2的烷基占40～100％，碳数3～4的烷基占0～60％，其流动点在-40℃以下，二液分离温度在-20℃以下，总酸值在0.02mg KOH/g以下，粘度在40℃以下时为8～100cst，粘度指数在80以上，
(式中，R1～R3可以相同或不同地各自表示氢原子或碳数1～8的烃基)。
另外，如权利要求2所述，所说氟代烃类致冷剂的纯度在99.5wt％以上，混入的含氯致冷剂在2000ppm以下。
另外，如权利要求3所述，在冷冻循环内的平衡水分[按下式(2)表示]在200ppm以下，
另外，如权利要求4所述，在冷冻循环内的残留氧量占冷冻循环内容积的0.2wt％以下。
另外，如权利要求5所述，在所说冷冻机油中具有相当于该冷冻机油0.01～1.0重量％的酚类防氧化剂作为必要成分，并配合有0.01～2重量％的环氧类或碳化二亚胺类化合物。
另外，如权利要求6所述，在所说的冷冻机油中配合有相当于该冷冻机油0.1～2重量％的磷酸酯类化合物。
另外，如权利要求7所述，所说的致冷剂是1，1，1，2-四氟乙烷(R134a)单体，或者是由50重量％的二氟甲烷(R32)与50重量％的五氟乙烷(R125)混合而成的共沸混合致冷剂，或者是由44重量％的五氟乙烷(R125)与52重量％的三氟乙烷(143a)以及4重量％的1，1，1，2-四氟乙烷(R134a)混合而成的拟共沸混合致冷剂。
另外，如权利要求8所述，在一个密闭容器内安置压缩机部件的同时，将HFC类致冷剂或其混合致冷剂以及与该致冷剂具有相溶性的冷冻机油封装入上述密闭容器内，上述冷冻机油以一种具有由下述通式(1)表示的构成单元的聚乙烯醚类化合物为主成分，并且在每一构成单元中，R4的构成比为，碳数1～2的烷基占80～100％，碳数3～4的烷基占0～20％，其流动点在-40℃以下，二液分离温度在-20℃以下，总酸值在0.02mg KOH/g以下，粘度在40℃以下时为8～100cst，粘度指数在80以上，
(式中，R1～R3可以相同或不同地各自表示氢原子或碳数1～8的烃基)。
另外，如权利要求9所述，其中所说的氟代烃类致冷剂的纯度在99.5wt％以上，混入的含氯致冷剂在2000ppm以下。
另外，如权利要求10所述，在冷冻循环内的平衡水分[按下式(2)表示]在200ppm以下，
Figure C9712297900071
另外，如权利要求11所述，在冷冻循环内的残留氧量占冷冻循环内容积的0.2wt％以下。
另外，如权利要求12所述，其中所说的致冷剂是由下述通式(3)表示的氟代烃物组中选择的至少2种的组合物构成，
      ClHmFn                   (3)
(式中，l＝1时，m＝1～2、n＝2～3，而且m+n＝4；l＝2时，m＝1～4、n＝2～5而且m+n＝6；l＝3时，m＝1～3、n＝5～7而且m+n＝8)。
另外，如权利要求13所述，其中所说的致冷剂是由50重量％的二氟甲烷(R32)与50重量％的五氟乙烷(R125)混合而成的共沸混合致冷剂，或者是由44重量％的五氟乙烷(R125)与52重量％的三氟乙烷(143a)以及4重量％的1，1，1，2-四氟乙烷(R134a)混合而成的拟共沸混合致冷剂。
另外，如权利要求14所述，在所说冷冻机油中具有相当于该冷冻机油0.01～1.0重量％的酚类防氧化剂作为必要成分，并配合有0.01～2重量％的环氧类或碳化二亚胺类化合物。
另外，如权利要求15所述，在所说的冷冻基油中配合有相当于该冷冻基油0.1～2重量％的磷酸酯类化合物。
另外，如权利要求16所述，在一个密闭容器内安置压缩机部件的同时，将HFC类致冷剂或其混合致冷剂以及与该致冷剂具有相溶性的冷冻机油封装入上述密闭容器内，上述冷冻机油以一种具有由下述通式(1)表示的构成单元的聚乙烯醚类化合物为主成分，并且在每一构成单元中，R4的构成比为，碳数1～2的烷基占60～100％，碳数3～4的烷基占0～40重量％，其流动点在-40℃以下，二液分离温度在-20℃以下，总酸值在0.02mg KOH/g以下，粘度在40℃以下时为8～100cst，粘度指数在80以上，
Figure C9712297900081
(式中，R1～R3可以相同或不同地各自表示氢原子或碳数1～8的烃基)。
另外，如权利要求17所述，其中所说的氟代烃类致冷剂的纯度在99.5wt％以上，混入的含氯致冷剂在2000ppm以下。
另外，如权利要求18所述，在冷冻循环内的平衡水分[按下式(2)表示]在200ppm以下，
Figure C9712297900082
另外，如权利要求19所述，在冷冻循环内的残留氧量占冷冻循环内容积的0.2wt％以下。
另外，如权利要求20所述，其中所说的致冷剂是由下述通式(3)表示的氟代烃物组中选择的至少2种的组合物构成，
        ClHmFn                   (3)
(式中，l＝1时，m＝1～2、n＝2～3而且m+n＝4；l＝2时，m＝1～4、n＝2～5而且m+n＝6；l＝3时，m＝1～3、n＝5～7而且m+n＝8)。
另外，如权利要求21所述，其中所说的致冷剂是由23重量％的二氟甲烷(R32)、25重量％的五氟乙烷(R125)和52重量％的1，1，1，2-四氟乙烷(R134a)混合而成的拟共沸混合致冷剂。
另外，如权利要求22所述，在所说冷冻机油中具有相当于该冷冻机油0.01～1.0重量％的酚类防氧化剂作为必要成分，并配合有0.01～2重量％的环氧类或碳化二亚胺类化合物。
另外，如权利要求23所述，在所说的冷冻机油中配合有相当于该冷冻机油0.1～2重量％的磷酸酯类化合物。
另外，如权利要求24所述，将致冷剂压缩机、冷凝器、减压装置、蒸发器用配管连接在一起，在上述密闭容器内封装入HFC类致冷剂或其混合致冷剂以及与该致冷剂具有相溶性的冷冻机油的同时，上述冷冻机油以聚乙烯醚类化合物为主成分，并且在每一构成单元中，R4的构成比为，碳数1～2的烷基占40～100％，碳数3～4的烷基占0～60％，其流动点在-40℃以下，二液分离温度在-20℃以下，总酸值在0.02mgKOH/g以下，粘度在40℃以下时为8～100cst，粘度指数在80以上，
(式中，R1～R3可以相同或不同地各自表示氢原子或碳数1～8的烃基)。
下面根据附图示出的实施例解释本发明
图1是旋转型压缩机的纵剖视图。在图1中，A是构成冷冻装置的冷冻循环，它由压缩机B、冷凝器C、减压装置D、蒸发器E、干燥器F通过配管连接而构成。其中，上述压缩机B具有如下结构。
1是密闭容器，在该容器内，上侧安装有电动单元2，下侧安装有由该电动单元驱动的旋转压缩单元3。电动单元2由定子5和设置在该定子内侧的转子6构成，该定子5具有由有机类材料绝缘的线圈4。旋转压缩单元3由气缸7、滚子10、叶片12、上部轴承13和下部轴承14构成，该滚子10由旋转轴8的偏心部9驱动沿着气缸7的内壁转动，叶片12由弹簧11推挤压接在该滚子的周面并将气缸7内部分隔为吸入侧和排出侧，上部轴承和下部轴承在封住气缸7的开口的同时，支承旋转轴8。
在上部轴承13处设置有与气缸7的排出侧相连通的排出孔15。另外，在上部轴承13处安装有用于开闭排出孔15的排出阀16，并安装有用于覆盖该排出阀的排出消声器(マフラ)17。
滚子10和叶片12皆由铁系材料制成。
在密闭容器1内的底部贮留有油18，该油如下述通式(1)所示是以聚乙烯醚类化合物作为主成分，在每一构成单元中，R4的构成比为碳数1～2的烷基占40～100重量％，碳数3～4的烷基占0～60重量％，其流动点在-40℃以下，二液分离温度在-20℃以下，总酸值在0.02mgKOH/g以下，粘度在40℃以下时为8～100cst，粘度指数在80以上，
(式中，R1～R3可以相同或不同地各自表示氢原子或碳数1～8的烃基)。
为了防止聚乙烯醚油在长期保存下的氧化劣化，向其中添加0.3wt％作为添加剂的2，6-二叔丁基对甲酚(DBPC)的酚类防氧化剂。另外，添加0.25wt％的环氧类添加剂作为化学稳定剂。
另外，根据需要，向所说多元醇酯油中加入1wt％的磷酸三甲苯酯(TCP)极压添加剂。
在冷冻循环A中封装入不含氯的氟代烃类致冷剂，例如R134a。
R134a的纯度为99.5wt％，将混入的含氯致冷剂调整至56ppm。另外，将冷冻循环A内的平衡水分(按下式(2)表示)调整至150ppm。
另外，在冷冻循环A使用的干燥器F中使用的水分吸附剂的孔径为3左右。将冷冻循环A内的残留氧量调节至占循环系统内容积的0.005wt％。
另外，在压缩机B的电动单元2中，线圈4被二层结构的绝缘材料包覆，其中，内侧施加由耐热聚酯(THEIC)或ェステルミド构成的膜层，外侧施加由酰胺-酰亚胺(アミドイミド)构成的膜层，另外，在线圈4之间等处使用一种低分子量(3聚体在0.6wt％以下)的PET薄膜作为绝缘纸来进行绝缘。
利用油18来润滑作为旋转压缩单元3的滑动部件的滚子10与叶片12的滑动面。
流入旋转压缩单元3的气缸7内并被滚子10和叶片12协同压缩的致冷剂由一种与多元醇酯类油的油18具有相溶性的R134a构成。
19是安装在密闭容器1内用于引导致冷剂至气缸7的吸入侧的吸入管，20是安装在密闭容器1上壁的排出管，它被旋转压缩单元3压缩通过电动单元而把致冷剂排出到密闭容器1之外。
关于在如此构成的旋转型压缩机中使用的冷冻机油组合物，来自吸入管19而流入气缸7内的吸入侧的致冷剂R134a被滚子10和叶片12协同地压缩，通过排出孔15并打开排出阀16而排出到排出消声器17内。在该排出消声器内的致冷剂通过电动单元2而从排出管20排出到密闭容器1之外。油18供应到旋转压缩单元3的滚子10和叶片12等的滑动部件的滑动面上，从而起润滑作用。另外，在气缸7内被压缩的致冷剂不会泄漏到低压侧区域。
按照本实施例，利用上述构成可以起如下作用。
根据权利要求1的构成，本发明的聚乙烯醚油18在冷冻装置A使用的全温度带内与R134a的相溶性都很好，致冷剂与油不会分成两层。
因此，在冷冻循环A中-30℃以下的低温区聚乙烯醚油18也一直以溶解于134a中的状态存在，并且其总体具有低粘度，因此，向压缩机B的回油性能良好。因此，压缩机B的油面不会降低，从而能确保向轴承滑动部件8、13、14的给油，并能防止咬死和烧伤。
而且，本发明的聚乙烯醚油18由于油本身的特性即具有提高压缩机B的轴8、轴承13、14的铁基滑动部件表面润滑性的作用，以及易溶于致冷剂(134a)中的作用，因此可以降低实际粘度，从而能减少机械损失并能提高压缩机B的工作效率。
另外，根据权利要求2的构成，使134a致冷剂保持很高的纯度，故在冷冻循环A中几乎没有异物和CFC混入，因此可以获得化学稳定性。
另外，根据权利要求3的构成，可以防止冷冻装置内的腐蚀，并能防止电动机绝缘材料(PET材料)的劣化。
另外，根据权利要求4的构成，可以防止由于聚乙烯醚油18的氧化劣化、聚合而产生淤渣，可以提供一种可靠性优良的冷冻装置。
另外，根据权利要求5的构成，可以提高聚乙烯醚油18的氧化劣化稳定性以及提高压缩机B的性能和可靠性。
这一点，也可以根据使用一种封装入添加了DBPC的本发明聚乙烯醚油18的密封管试验的实验结果来确认。
也就是说，进行90℃×29天的老化试验，在将水分调整至200ppm的条件下，使用添加了DBPC的本发明的聚乙烯醚油18，由此在初期阶段，其总酸值在0.01以下，获得了良好的结果。
另外，根据权利要求6的构成，可以在轴承滑动面8、10、13、14上形成牢固的化学吸附膜，由于滑动部件8、10、13、14的润滑性更加良好，因此可以防止咬死和烧伤。
以上的作用效果也可根据图2所示的装置进行的耐久试验结果来确认。
也就是说，以耐久试验的时间作横轴，以污垢量(淤渣量)作纵轴制成图2的曲线，使用加入了添加剂(DBPC、环氧化合物等)的本发明聚乙烯醚类油18的试料Y，装置的制造基准按照本发明所限定的基准B(限定了致冷剂的纯度、冷冻循环A内的水分、氯、空气量)的试料IV获得了最佳的结果。
另外，在图2中，有关试料I～IV的内容如下。
           表 1
  添加剂   制造基准
    I     无     A
    II     X     A
    III     Y     A
    IV     Y     B
其中，添加剂 X：DBPC+BTA+TCP
      添加剂 Y：DBPC+BTA+TCP+环氧化合物
      制造基准A：(以往的基准)
致冷剂的纯度：99.90wt％
      冷冻循环A内的平衡水分量：600ppm
      冷冻循环A内的残留空气量：0.03wt％
      冷冻循环A内的氯残留量：400ppm
      制造基准B：(本发明的基准)
致冷剂的纯度：99.95wt％
      冷冻循环A内的平衡水分量：200ppm
      冷冻循环A内的残留空气量：0.01wt％
      冷冻循环A内的氯残留量：100ppm
另外，在本实施例中，举出R134a作为不含氯的氟代烃致冷剂的例子进行说明，但是不限于该例子，本发明的多元醇酯类油对于其他的HFC致冷剂也具有很优良的相溶性，因此也适用于这些致冷剂。
另外，图3中示出了作为本发明另一个实施例的止转棒轭式往复动型压缩机。图3示出了其总体构成，其中，110是压缩机，111是用于压缩致冷剂的机构部，112是壳体，113是悬挂弹簧。另外，114是构成电动机部(压缩机的电动单元)的定子，115是定子固定螺栓，116是合成橡胶垫圈。
117是由压缩机本体的框架构成的定子安装基座，118是曲轴。另外，在定子114与转子之间设置为了驱动常规压缩机中作为电动单元的转子所需的间隙。
压缩机本体由用于带动上述机构部111的电动机部构成，如图3所示，压缩机本体由悬挂弹簧113悬挂在壳体112中。
另外，定子114通过上述的合成橡胶垫圈116被几个定子固定螺栓115固定在定子安装基座117上。
如上所述，按照本发明，将特定的原料作为聚乙烯醚油、在特定的物性范围内使用并向其中加入特殊的添加剂，同时将氟代烃类致冷剂的纯度维持在高的数值并且抑制在冷冻循环中的平衡水分，这样就能降低聚乙烯醚类油的总酸值并抑制金属皂的生成，从而能够防止对冷冻循环产生的不良影响，并能抑制由于氧或氯的影响而产生的分解、氧化劣化和聚合反应，以及能够防止金属皂和高分子淤渣的生成，从而可以获得良好的冷冻装置。
对附图的简单说明
图1是表示本发明一个实施例的旋转型压缩机的纵剖视图。
图2是表示冷冻装置实机耐久试验结果的曲线图。
图3是表示本发明另一个实施例的往复动式压缩机的纵剖视图。
图中符号的说明：
     A         冷冻装置
     B         旋转压缩机
     F         干燥器
     1         密闭容器
     3         旋转压缩单元
     10        滚子
     12        叶片
     18        油
     110       往复动型压缩机
     114       定子
     115       定子固定螺栓
     116       合成橡胶垫圈
     117       定子安装基座

Claims (10)

1.一种冷冻装置，包括安置在密闭容器内的压缩机部件，在密闭容器内封装有氟代烃类致冷剂或其混合致冷剂以及与该致冷剂具有相溶性的冷冻机油，其中所述冷冻机油以具有下式(1)的构成单元的聚乙烯醚类化合物为主要成分，其流动点在-40℃以下，二液分离温度在-20℃以下，总酸值在0.02mg KOH/g以下，粘度在40℃以下时为8～100cst，粘度指数在80以上，其中n为1以上的整数，R1～R3可以相同或不同，各自表示氢原子或碳数1～8的烃基，R4为2-3个碳原子的烷基，并且其中R4为2个碳原子的烷基的单元占聚乙烯基醚化合物的80-100％，R4为3个碳原子的烷基的单元百分数为聚乙烯基醚化合物的20％以下。
2.根据权利要求1的冷冻装置，其特征在于，其中所说的氟代烃类致冷剂的纯度在99.5wt％以上，混入的含氯致冷剂在2000ppm以下。
3.根据权利要求1的冷冻装置，其特征在于，在冷冻循环内的平衡水分按下式(2)表示在200ppm以下，
Figure C9712297900022
4.根据权利要求1的冷冻装置，其特征在于，在冷冻循环内的残留氧量占冷冻循环内容积的0.2重量％以下。
5.根据权利要求1的冷冻装置，其特征在于，其中所说的致冷剂是由下述通式(3)表示的氟代烃物组中选择的至少2种的组合物构成，
     ClHmFn                            (3)
式中，l＝1时，m＝1～2、n＝2～3而且m+n＝4；l＝2时，m＝1～4、n＝2～5而且m+n＝6；l＝3时，m＝1～3、n＝S～7而且m+n＝8。
6.根据权利要求1的冷冻装置，其特征在于，其中所说的致冷剂是由50重量％的二氟甲烷(R32)与50重量％的五氟乙烷(R125)混合而成的共沸混合致冷剂，或者是由44重量％的五氟乙烷(R125)、52重量％的三氟乙烷(143a)以及4重量％的1，1，1，2-四氟乙烷(R134a)混合而成的拟共沸混合致冷剂。
7.根据权利要求1的冷冻装置，其特征在于，在所说冷冻机油中具有相当于该冷冻机油0.01～1.0重量％的酚类防氧化剂作为必要成分，并配合有0.01～2重量％的环氧类或碳化二亚胺类化合物。
8.根据权利要求3的冷冻装置，其特征在于，在所说的冷冻机油中配合有相当于该冷冻机油0.1～2重量％的磷酸酯类化合物。
9.根据权利要求1的冷冻装置，其特征在于，其中所说的致冷剂是由23重量％的二氟甲烷(R32)、25重量％的五氟乙烷(R125)和52重量％的1，1，1，2-四氟乙烷(R134a)混合而成的拟共沸混合致冷剂，或是由25重量％的二氟甲烷(R32)、15重量％的五氟乙烷(R125)和60重量％的1，1，1，2-四氟乙烷(R134a)混合而成的拟共沸混合致冷剂。
10.根据权利要求1的冷冻装置，包括致冷剂压缩机、冷凝器、减压装置、蒸发器，通过配管连接。
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